Charged Colloids The generation of colloidal charges in water. The theory of the diffuse electrical double-layer. The zeta potential. The flocculation of charged colloids. The interaction between two charged surfaces in water. Laboratory project on the use of microelectrophoresis to measure the zeta potential of a colloid. The formation of charged colloids in water Most solids release ions to some extent when immersed in a high- dielectric-constant liquid such as water. Even oil droplets and air bubbles have a significant charge in water. In order for this charging process to take place ions must dissociate from the surface, which will then be of opposite charge. (Note that the charge could equally well be created by the selective adsorption of a particular ion from solution.) Let us con- sider the work required to separate an ion pair in vacuum (or air) and in a high-dielectric-constant liquid, such as water. This situation is illus- trated in Figure 6.1. D is the static dielectric constant of the medium, which is given by the ratio of permittivities of the medium (e) and of free space (£9). From Coulomb’s law for two charges, q; and qo, separated by distance r, the attractive force F, is given by the relation: Applied Colloid and Surface Chemistry Richa ‘and Mati E. Karaman SPF Seyi Sc, i ISBN0 40 ddd 1 a) 0470 Seb X TFB)4 CHARGED COLLOIDS D=1 (ait) D= 80 (water) Yd X44 Figure 6.1 Diagram illustrating the ionization of a surface in air and water. «ih 6.1 4nDe,r” (6-1) where the force F, is attractive (negative) between unlike charges. As a first approach, we can easily estimate the work (W.) required to sepa- rate two charges from close separation of, say, 2A to a large distance by integration of (6.1). In water, where D = 80, this work is about 6 x 1071J, which is quite close to the kinetic energy of the free ion (i.e. kT). However, if the medium was air or vacuum (D = 1), the work required would be about 100kT. Clearly, it is the high dielectric con- stant or polar nature of water which allows this ion dissociation to occur, whereas in air and non-polar liquids (e.g. D ~ 2 for liquid hexane) we would expect no dissociation. It is for this reason that we are mostly interested in charging processes at the solid/aqueous inter- face and the stability of colloids, which often become charged when dispersed in aqueous media. The theory of the diffuse electrical double-layer Although the single ion dissociation approach gives a good indication of the basic conditions for dissociation, the real situation is more com- plicated because there will usually be a high density of ions dissociated from the surface. This will introduce repulsive forces between the dis- sociated ions and a much stronger attraction back to the surface, because of the high electric field generated there. In fact, the electric field generated at the surface prevents the dissociated ions from leaving the surface region completely and these ions, together with the charged‘THE THEORY OF THE DIFFUSE ELECTRICAL DOUBLE-LAYER 95 diffuse layer bulk electrolyte solution (electroneutral) e| o : Zo fo ft 6 7g/° o} ° za, © © 1 © 9 70} 25: 0 7geo 88) % 6 72 0 © 1 © © Zo o |} 7,9) 6 1 @ ° a { ¢ ' solid. i jueous lution Figure 6.2 The diffuse electrical double-layer in aqueous solution next to a flat surface. surface, form a ‘diffuse electrical double-layer’, as illustrated in Figure 6.2. In order to understand the diffuse layer in detail, we need to go back to the fundamental equations of electrostatics due to J.C. Maxwell. The equation of interest relates the local electric field E(7) at the position vector 7 to the net local electric charge density p(7): W8g)= 20 (6.2) Thus, the divergence or flux of the electric field is directly related to the net charge at that point. The electric field is simply defined as the force acting on a unit charge: (6.3) The limit is required because otherwise a finite test charge ‘q’ would itself perturb the electric field. Clearly, from (6.3), the direction of the electric field is that taken by a positive charge when free to move. Because the electric field is a vector, it is often more useful to use the corresponding electrostatic potential (7), which is a scalar quantity and is defined as the potential energy gained by moving a unit charge from infinity to the position 7. The potential energy of an ion of chargeCHARGED COLLOILs 96 Figure 6.3 The one-dimensional case of a flat surface. Zq at 7 is therefore simply given by Z,qy(7), where q is the proton charge and Z; the valency of the ion. Note that if the potential is pos- itive, then a positive charge will have an increased (positive) potential energy compared with that at infinity. Since y(7) is the electrostatic potential energy per unit charge, the gradient of this parameter with distance must be equal to the force acting on a unit charge - which is the definition of the electric field. Hence it follows that EG)=-Vy) (6.4) In order to simplify (6.2), let us consider the common case of the electric field generated by a charged, flat surface (such as an electrode), see Figure 6.3. For this case and using electric potentials (6.2) becomes 2, ve) I = = (6.5) where y and p are now only functions of x, the distance from the flat surface. To solve this equation we need to find the relationship between p(x) and w(x). The local density of any ion of charge Zq (which can be either positive or negative) must depend on its electrostatic poten- tial energy at that position (i.e. at x). From our definition of y this potential energy is given by Z,qy(x). Since any ion next to a charged surface must be in equilibrium with the corresponding ions in the bulk solution, it follows that the electrochemical potential of an ion at dis- tance x from the surface must be equal to its bulk value. Thus: wh suf =p! +47 InG,(B)=p? +Z,qy(2)+kT InG\(x)‘THE THEORY OF THE DIFFUSE ELECTRICAL DOUBLE-LAYER 97 where C(B) and C(x) are the ion concentrations in bulk and at dis- tance x from the charged surface, and it is assumed that these are dilute solutions (i.e, y(B) = 0). This equation leads directly to the Boltzmann distribution, which can be used to obtain the concentration at any other electrostatic potential energy by the familiar relationship C(x) = C\(B) ex 2q¥)| (6.6) This result is very useful because it gives us the concentration of any ion next to a charged surface when immersed in an electrolyte solution. We can also use this result to obtain the net charge density (due to both counterions and co-ions) at a distance x from a charged surface: (x) = D,ZqCi(x) = Y,ZaCi(B) eof =A | (6.7) and substitution in (6.5) then gives the result Py(x)__g ~Zaqu(x) Tea FUL zC@en[ AMO] This is the important ‘Poisson—Boltzmann’ (PB) equation and the model used to derive it is usually called the ‘Gouy-Chapman’ (GC) theory. It is the basic equation for calculating all electrical double-layer prob- lems, for flat surfaces. In deriving it we have, however, assumed that all ions are point charges and that the potentials at each plane ‘x’ are uniformly smeared out along that plane. These are usually reasonable assumptions. ‘We can now set about using (6.8) to give us information about the quantitative details of the electrical double-layer. Let us, for simplicity, assume that the electrolyte in which the surface is immersed is sym- metrical, that is a Z:Z electrolyte (ie. 1:1, 2:2 or 3:3, where Z = 1, 2 or 3). Equation (6.7) then becomes ols) =24C(By{exe{=2222)|—exp{ 2248)98 CHARGED COLLOIDS and if we, for convenience, define Y = Zqy(xV/kT this reduces to p(x) = -ZqC(B){exp(Y) - exp(-Y)} p(x) = -2ZqC(B)sinh(Y) (6.9) which in the PB equation (6.8) gives 1 tat SVG) 2270) sinny) (6.10) " (Note that for symmetrical electrolytes C(B) = C{(B).) Now, for convenience (and not arbitrarily, as will be seen later), let us replace the real distance x with a scaled distance X, such that X =x and «*, which is called the Debye length, is defined as: v2 5 -(ascual (6.11) The useful parameter x has the units of length and depends on both the electrolyte type and concentration. Scaling x in (6.10) thus gives the deceptively simple, non-linear, second-order differential equation SyosinhY (6.12) Integration of (6.12) gives the potential distribution next to a charged surface: y=2 [tise 6.13) 1-yexp(-X) 1 ea where _[exp(¥o/2)=1 a al and Yp is the scaled electrostatic potential at the surface of the charged plane (i.e. at x = 0, w= Wo and at X = 0, -Y = Yo). This result gives usTHE DEBYE LENGTH 99 a great deal of information about the decay in potential and hence the distribution of all ionic species in the diffuse electrical double-layer next to a charged, flat sur! The Debye length We can easily get some idea of what this theory predicts by looking at the limit of low potentials, that is where Yy « 1 (which for 1:1 elec- trolytes corresponds to Wo < 25 mV). In this case (6.13) can be shown to reduce to the simple result W(%) = Wo exp(-Kx) (6.14) which demonstrates the physical meaning of the Debye length. This length is also referred to as the ‘double-layer thickness’ and, from (6.14), it obviously gives an indication of the extent of the diffuse layer. It is the distance from the surface where the surface potential has fallen to 1/e of its original value. Equation (6.14), although approximate, enables us to estimate the decay in electrostatic potential away from a flat, charged surface. Some typical results are shown in Figure 6.4. These results clearly demonstrate the effect of electrolyte concentration 120: 3 langt «30s Electrostatic potential / mv 3 40, 20 0 -——4 0 5 10 15 20 25 30 35 40 Distance, x/nm Figure 6.4 Estimates of the decay in electrostatic potential away from a charged flat plate in a range of electrolyte solutions.100 CHARGED COLLOIDS Ce eee 3 Cl Ion cone / mM 8 8 0 5 10 ot 20 25 30 35 40 Distance from flat surface, x/nm Figure 6.5 Estimates of the Ce” counter-ion concentrations away from a flat, charged surface of potential +100 mV. on screening the range of the surface electrostatic potential. In each case the Debye length is equal to the distance from the surface at which the surface potential has fallen to 100/e or 37mV. (Note that use of (6.13) gives a more accurate potential distribution.) Once the potential distribution next to a charged surface is known the Boltzmann distribution (6.6) can be used to calculate the corre- sponding distribution of both counter-ions and co-ions, in an elec- trolyte solution next next to a charged surface. The results obtained for both counter-ions and co-ions are given in Figures 6.5 and 6.6 for a monovalent electrolyte solution, e.g. NaCl electrolyte at mM concen- tration next to a +100 mV flat surface. Using the relatively simple equa- tions derived above it is clearly possible to obtain precise details about the ion distributions next to charged, flat surfaces when they are immersed in electrolyte solutions. This information is crucial to a thorough understanding of the properties of electrodes, colloidal solutions and soil chemistry. As might be expected, counter-ions are pulled towards surfaces of opposite charge, reaching quite high concentrations close to the surface. By comparison, co-ions are expelled by the same-charge surface and form a depleted layer. Similar results can be obtained using a combination of mixed and multi-valent electrolytes.THE SURFACE CHARGE DENSITY 101 Nas Jon cone / mM ° Fy «0 60 0 100 120 Distance from flat surface, x/am Figure 6.6 Estimates of the Na‘ co-ion concentrations away from a flat, charged surface of potential +100 mV. The surface charge density So far we have talked only in terms of electrostatic potentials. Can we use this theory to find the charge density on the surface (6)? In order for the electrical double-layer to be neutral overall, it follows that the total summed charge in the diffuse layer must equal the surface charge. Thus, it follows that 6p =~00 = fo(x)dx (6.15) 0 where Gp is the total diffuse layer charge. Now, since from (6.5), dy(x) _ -p(x) de? eD (6.5) it follows that =epit Vax Op eeDf + and hence102 Maer 6) = 20D YE] (6.16) since dy(x)/dx = 0 as x -» e, Now we can integrate (6.8) using the fact that : ; [Say= w/2( 2) +C (6.17) and using various known boundary conditions obtain the first-order differential equation due). (25, Cale no(- Zav(e)) _ -}" (6.18) which on substitution into (6.16) gives the result Go = (sgn wo){2eDeT Yc exo{-22¥2) - ip" (6.19) which, for a 1:1 electrolyte reduces to 6» = [BEgDRTC(B)]"” snn( $22.) (6.20) Hence, the surface charge can be easily calculated from the surface potential for a planar surface. The zeta potential The stability of many colloidal solutions depends critically on the mag- nitude of the electrostatic potential (wo) at the surface of the colloidal particles. One of the most important tasks in colloid science is there- fore to obtain an estimate of o under a wide range of electrolyte con- ditions. In practice, one of the most convenient methods for obtaining Wo uses the fact that a charged particle will move at some constant, lim- iting velocity under the influence of an applied electric field. Even quite small particles (i.e. <1}1m) can be observed using a dark-field micro-THE HUCKEL EQUATION 103 scope and their velocity directly measured. This technique is called microelectrophoresis and what is measured is the electromobility ({1) of a colloid, that is its speed (u) divided by the applied electric field (E). Let us now examine how we can obtain an estimate of wo from the measured electromobility of a colloidal particle. It turns out that we can obtain simple, analytic equations only for the cases of very large and very small particles. Thus, if a is the radius of an assumed spher- ical colloidal particle, then we can obtain direct relationships between electromobility and the surface potential, if either xa > 100 or ka < 0.1, where x" is the Debye length of the electrolyte solution. Let us first look at the case of small spheres (where xa < 0.1), which leads to the Hiickel equation. The Hiickel equation (ka < 0.1) The spherically symmetric potential around a charged sphere is described by the Poisson—Boltzmann equation: id iv) 00) fe ral dr} eD (6.21) where p(r) is the charge density and y the potential at a distance r away from a central charge. This equation can be simplified using the Debye- Hiickel or linear approximation valid for low potentials: 1 dfadi 33° *| ay (6.22) which has the simple, general solution: ys Sent 4 Hevice) (6.23) The constant A must equal zero for the potential w to fall to zero at a large distance away from the charge and the constant B can be obtained using the second boundary condition, that y = yo at r = a, where a is the radius of the charged particle and Yo the electrostatic potential on the particle surface. Thus we obtain the result that104 CHARGED COLLOIDS B & me exot xr) (6.24) and, therefore vy = MotexplK(r- a] (6.25) r The relationship between the total charge q on the particle and the surface potential is obtained using the fact that the total charge in the electrical double-layer around the particle must be equal to and of opposite sign to the particle charge, that is: q=—[4nr°p(r)dr (6.26) where p(r) is the charge density at a distance r from the centre of the charged particle. The value of p(r) can be obtained from combination of (6.21) and (6.22), assuming the linear approximation is valid and hence q= 4negDx? | r>ydr (6.27) Now, using (6.25) for w, q= 4neqDx?ayfrexpl—x(r—a)]|dr (6.28) Integration using Leibnitz’s theorem gives: q = 4ne:Dayy(1+Ka) (6.29) and rearranging this equation leads to a useful physical picture of the potential around a sphere, thus: 4 q “GnDega 4nDeg(a+) (6330) Vo105 -e-- Figure 6.7 Diagram of the diffuse electrical double-layer around a small, charged colloid. This result corresponds to a model of the charged particle with a diffuse layer charge (of opposite sign) at a separation of 1/k, as illustrated in Figure 6.7. Since we now have (6.29) which relates the charge on the particle to the surface potential, we can combine this with the forces acting on a moving particle in an applied electric field. Thus, when the particle is moving at constant velocity (#) the electrostatic force on the particle (gE) must equal the drag force, which we may assume (for laminar, steady fluid flow) to be that given by Stokes’s law (i.e. Farag = 6Maun). Using (6.29) and the fact that we define the electromobility (11) of a particle as u/E, we obtain the result that __ 3 Wor 2e,D(1+ Ka) (631) which for xa « 1 becomes: =. 05a 78 (6.32) In this result, the condition of small particles means that the actual size of the particles (which is often difficult to obtain) is not required. For reasons to be discussed later, we will call the potential obtained by this method the zeta potential (¢) rather than the surface potential. In the following section we consider the alternative case of large colloidal par- ticles, which leads to the Smoluchowski equation.CHARUED LULLoN nACAV, fae) L 106 AreaA MAGVIdx), + + O=p.Adx Figure 6.8 Schematic diagram of the balance in forces acting on a fluid element close to the surface of a large colloidal particle. The Smoluchowski equation (Ka > 100) Let us now consider an alternative derivation for the case of large col- loidal particles, where the particle radius is much larger than the Debye length (i.e. ka > 100). The situation is best described by the schematic diagram, Figure 6.8, where the surface of the large particle is assumed to be effectively flat, relative to the double-layer thickness. It is also assumed, in this approach, that the fluid flows past the surface of the particle in parallel layers of increasing velocity with distance from the surface. At the surface the fluid has zero velocity (relative to the parti- cle) and at a large distance away, the fluid moves with the same veloc- ity as the particle, but in the opposite direction. It is also assumed that the flow of the fluid does not alter the ion distribution in the diffuse double-layer (i.e. in the x direction). Under these conditions mechani- cal equilibrium can be considered in a fluid element between x and x + dx, when the viscous forces acting in the z direction on the fluid element, due to the velocity gradient in the x direction, are precisely‘THE SMOLUCHOWSKI EQUATION 107 balanced by the electrostatic body force acting on the fluid due the charge contained in it. Thus, we obtain the mechanical equilibrium con- dition that av, av, E,pyAdx = na) = na(“2e) . (6.33) or , E,p,Adx = -na = oe (6.34) ‘We can then relate the charge density, p,, to the electrostatic potential using the one-dimensional Poisson-Boltzmann equation, ay Pe a) (6.35) Thus, in (6.34): aA E, eo SM de = (2 aa ie (6.36) which on integration gives dy _ (dv, E.eDe= o( e 4a (6.37) Since dy/dx = 0 when dV,/dx = 0, the integration constant, c, must be equal to zero and a second integration, 7 d dv, [Cees ede = fo Fei (6.38) produces the result that E,£9D¢ =-nV, (6.39) if it is assumed that D # f(x) and 1 # fix) (ie. that the fluid is Newtonian). Since -V, refers to the fluid velocity we can easily convert108 CHARGED COLLOIDS (6.39) to particle velocity (i.e, Vp =-V,) and from our definition of elec- tromobility (jt) it follows that A 6.40 eD (6.40) This important result is called the Smoluchowski equation and, as before, the zeta potential is directly related to the mobility and does not depend on either the size of the particle or the electrolyte concentration, Tn summary, for the two extreme cases, we have: “ep for ka «1(<0.1) sep? for ka >>1 (>100) Corrections to the Smoluchowski equation These equations have been shown to be correct under the conditions of electrolyte concentration and particle size stated. However, it is easy to show that using typical colloidal sizes and salt concentrations, many colloidal systems of interest, unfortunately, will fall between the ranges covered by these equations. In deriving both the Hiickel and Smolu- chowski equations we have, for simplicity, ignored ‘relaxation’ and ‘electrophoretic retardation’ effects, which have to be included in a more complete theory. The origin of these effects is illustrated in Figure 6.9, which shows a solid, charged particle moving in an electric field. Ee«# — Counter- ion cloud Figure 6.9 Diagram of a charged colloid moving in a fluid under the action of an electric field.CORRECTIONS TO THE SMOLUCHOWSKI EQUATION 109 When in motion, the diffuse electrical double-layer around the particle is no longer symmetrical and this causes a reduction in the speed of the particle compared with that of an imaginary charged particle with no double-layer. This reduction in speed is caused by both the electric dipole field set up which acts in opposition to the applied field (the relaxation effect) and an increased viscous drag due to the motion of the ions in the double-layer which drag liquid with them (the elec- trophoretic retardation effect). The resulting combination of electro- static and hydrodynamic forces leads to rather complicated equations which, until recently, could only be solved approximately. In 1978, White and O’Brien developed a clever method of numerical solution and obtained detailed curves over the full range of xa values (0 > ©) and surface potentials, At intermediate values of xa the relationship between € and 1 is non-linear and strongly dependent on electrolyte type (i.e, charge and ion diffusion coefficients), A computer program is available from these authors to enable calculation of the zeta potential for any common electrolyte. With the successful introduction of this precise numerical procedure the onus is now on experimentalists to carry out well-defined mobility measurements on ideal, spherical par- ticles of accurately known size. Figure 6.10 shows the non-dimensional electrophoretic mobility as a function of zeta potential, for a range of xa values, corrected for these two factors. The curves represent computed values obtained by White and O’Brien, while the broken lines are the thin double-layer approxi- mation. The ka = line is Smoluchowski’s result. (See also the stand- ard text Zeta Potential in Colloid Science by R.J. Hunter, 1981.) Finally, let us return to the problem of relating the measured zeta potential to the defined surface potential. The zeta potential is always measured (by definition) in an electrokinetic experiment. In this case the fluid has to flow around the particle. We expect, however, that a certain thickness of fluid (of roughly molecular dimensions) will remain stationary with respect to the particle, due to the large amount of work required to move fluid molecules along a solid surface. Obviously there will not be a sharp cut-off at say one or two molecular layers but a gradual increase in fluid flow will occur away from the particle. Since the total charge on the solid particle is responsible for the surface poten- tial, the measured value, zeta, is generally of slightly lower magnitude. As we will see later, a better estimate of the surface potential can be obtained from direct interaction force measurements, and values so obtained can be compared with electrokinetic measurements, on exactly the same system in some cases (such as for muscovite mica).110 CHARGED COLLOIDS nep/ekT 10 3 C=eC/ekT Figure 6.10 Theoretical calculations of the corrections required for the zeta potention ({) from electromobility (4) values. Some systems do show excellent agreement between zeta and the surface potential, whilst others differ significantly. Since no definitive results have yet been obtained, it is perhaps best to assume as a first approximation that these two potentials are similar. The zeta potential and flocculation A good example of the use of microelectrophoresis experiments is sup- plied by the study of ferric flocs, which are widely used in municipal Water treatment plants, The zeta potentials shown below were derived from the measured floc electromobilities using the Smoluchowski equa-THE ZETA POTENTIAL AND FLOCCULATION 1 60 40-4 meet Lins a - § 20 5 & a9 bot -20. > 3.3mg/L 33mg/L -40. — 2 3 4 SS 7 8 9 10° 41 pH Figure 6.11 The zeta potential of ferric flocs as a function of concentration and PH. tion. Figure 6.11 shows the effect of pH on the zeta potential of ferric flocs generated by precipitation of 3.3mg/L (20HM) and 33mg/L (200M) ferric chloride in mM sodium chloride solution. Since almost all colloidal contaminants in natural water systems are negatively charged, it is important to operate under pH conditions where the flocs are positively charged, that is at pH values above the isoelectric point (iep, where the particles are uncharged). Under these conditions, the flocs have an electrostatic force attracting the contaminant particles to the flocs. The large flocs, containing adsorbed contaminants, are then sedimented and collected via filtration through high-flow-rate sand-bed filters. Unfortunately, in practice, ferric chloride usually contains man- ganese as a contaminant and this necessitates precipitation at pH values between 8 and 9, to prevent manganese dissolution, which will colour the drinking water. The use of these higher pH values means that poly- cationic, water-soluble polymers are often added, which adsorb on to the ferric flocs and increase their iep.CHARGED COLLOIDS 112 MQXitX&™(SOOOOXVA non-interacting surfaces, d>>K! Amat, Zz Vo % % 4 Z Ga 4 7 % Z Z Z Z pear pana interacting surfaces, d 1). This method was developed by Derjaguin.116 CHARGED COLLOIDS Figure 6.13 Diagram used to explain the Derjaguin approximation for the interaction between two spheres. The Derjaguin approximation A schematic diagram of the analysis method used is given in Figure 6.13. In this procedure, called the ‘Desjaguin approximation’, we con- sider the interaction of the circular annulus (dx) with an imaginary parallel surface plane at distance Z. With this assumption, the total interaction energy V, between the spheres is then given by Ve=2nf Vexde (6.50) From simple geometry we can easily rearrange this equation in the form V,= nal. Vidz (6.51) Using the result given in (6.49), we can then obtain the corresponding interaction energy between spheres: V, = 2nae,Dy3 exp(-xH) (6.52) Once again the interaction energy decays exponentially and is strongly dependent on both the surface potential and the electrolyte concentration.Industrial Report The use of emulsions in coatings From 2000 8c, when decorative paintings adorned the walls of Egyptian tombs, all the way up through much of the:1900s, little changed in. the rudimentary approach to formulating décorative or. protective’ paints. Paints were based on naturally , occurring oleoresinous materials: combi- nations of naturally occurring drying oils and resins. Linseed oil became the most widely used oil, while amber. was the most common resin. Even-118 CHARGED COLLOIDS mers, which act as resin support for the growing polymer particles. Also, many coatings emulsion polymers contain lonic groups, which gohan sta- : bility via contributing to an electrical double-layer. 1 Commercially significant coatings emulsions includ Relics copoly: mers of acrylates, such as butyl acrylate, and methacrylates, such as methyl | methacrylate; styrene-acrylics: copolymers of styrene with an acrylate m=-nomer; and vinyl-acetate polymers: homopolymers of inyl acetate, or | copolymers with softer Monomer such as ethylene o} at Polymers which are 100% acrylic are known for thel ior durability mips as well as excellent alkali re:120 CHARGED COLLOIDS: 6. The surface of a colloid dispersed in aqueous salt solution was found to have an equilibrium surface electrostatic potential of +80mV, due to the specific adsorption of Na* ions, What is the (chemical) free energy of adsorption of Na’ ions to this surface? 7. Simplify (6.13) to give a simple physical interpretation of the Debye length. 8. Estimate the concentration of Na’ ions at the centre layer of an aqueous soap film drawn from a mM NaCl solution, if the elec- trostatic potential at each surface is -20mV and the film is 10nm thick. 9. The electrostatic potential at a distance of Snm away from a charged, flat surface was found to be -10mV in an aqueous 0.1mM NaCl solution. Estimate the electrostatic potential at the surface. What are the concentrations of each ion at this distance away from the surface? Estimate the osmotic pressure at this plane. Experiment 6.1 Zeta potential measurements at the silica/water interface Introduction The stability of most colloidal solutions depends critically on the mag- nitude of the electrostatic potential (yo) at the surface of the colloidal particle. One of the most important tasks in colloid science is therefore to obtain an estimate of Wo under a wide range of electrolyte condi- tions. In practice, the most convenient method of obtaining Yo uses the fact that a charged particle will move at some constant, limiting veloc- ity under the influence of an applied electric field, Even quite small par- ticles (i.e. <1 jm) can be observed using a dark-field illumination micro- scope and their (average) velocity directly measured. The technique is called ‘microelectrophoresis’. At low electric fields [O(1 V/cm)] the speed (U) of the particles is directly proportional to the applied field (E) and hence we can define a parameter called the electromobility (1) of the particles, given by U/E. Using the Poisson-Boltzmann theory of the diffuse electrical layer next to a charged surface, a simple relationship between 1 and wo can beEXPERIMENT 6.1 ZETA POTENTIAL MEASUREMENTS 124 derived, However, because of doubts about the validity of the theory we introduce another surface potential called the ‘zeta potential’ (C) to represent the surface potential obtained from the electromobility meas- urements. This potential corresponds to the electrostatic potential at the plane of shear in the liquid, which is assumed to be close to the particle’s surface, (Note that in general it usually reasonable to assume that Wo = G) This potential is given by the Smoluchowski equation oH, $= =D (6.53) where 1 is the viscosity of the solution, e9 the permittivity of free space and D the dielectric constant. It is important to note that because of the method of derivation of this equation it is only valid for colloidal particles which are large compared with the Debye length (x) of the electrolyte solution (i.e. ka >> 1, where a is the radius of the colloidal particles), In general, therefore, this equation will be valid for particles of 1pm or larger radius. The surface of a silica (or glass) particle contains a high density of silanol groups (about 1 per 25 A?) which dissociate to some extent in water to give a negatively charged surface, Figure 6.15. The magnitude of the electrostatic potential at the silica surface is, as expected from the law of mass action, pH-dependent. The variation in surface (or zeta) potential with pH must therefore be dependent on the dissociation constant of the surface silanol (Si-OH) group. In this experiment a ‘zeta-meter’ is used to determine the variation in the zeta potential of silica at constant pH (5.7) over a range of con- centrations of a cationic surfactant CTAB, which should adsorb on the ionized silanol groups on the silica particle surface. #,0 silica 1,0 H,0 OO HAY 4 SOY! AXOyn b Figure 6.15 lonization of the surface of silica in water.SAMPLE PROBLEMS 119 Sample problems 1. Calculate the Debye lengths for 0.1mM, 10mM and 100mM aqueous solutions of NaCl and MgSO,, assuming that the salts are completely ionized. Calculate and graph the concentration profiles for Na* and Cl" ions next to a planar charged surface with a potential of -85mV immersed in a 10mM NaCl solution. Show graphically how the surface charge density varies with the surface potential for a planar surface in different Debye-length solutions. Use the superposition principle to calculate the electrostatic swelling pressure generated between parallel clay platelets with surface potentials of -110mV, at a separation of 35nm in a 1.5mM aqueous solution of NaCl at 25°C. Estimate the thickness of a water film of 0.1mM NaCl solution on a glass plate, 1cm above a water reservoir. Assume that the water completely wets the glass and that the water/glass interface has an electrostatic potential of -60mV and that only gravitational and electrical double-layer forces need be considered. Also assume that there is no surface charge at the water/air interface.122 CHARGED COLLOIDS convergent . Tens ree! ea 1) = —>4 Com > \ \ colloidal solution centre light inside rectangular stop silica cel Figure 6.16 Diagram of the dark-field illumination system used to visualise colloidal particles in water. Experimental details This experiment is based on the use of a classic Rank Bros (Cambridge, UK) Mark 2 microelectrophoresis apparatus, which is based on the manual microscopic observation of the speed of colloids, detected by dark-field illumination, under the action of an applied electric field. Either a rectangular or a cylindrical quartz cell can be use. For a com- prehensive reference text, see R.J. Hunter, The Zeta Potential (1981). Before using the zeta-meter apparatus make up colloidal solutions of silica using about 0.01 g solid per 100 mL of a range of CTAB solutions from 10*M to 107M, in 107M KBr (to keep the Debye length con- stant), Always shake these solutions thoroughly before transferring to the apparatus cell. An illustration of the illumination used in this type of apparatus, to observe the motion of colloid particles, is given in Figure 6.16. Basi- cally, the illumination system and microscope allow you to observe the motion of the silica particles, which are seen as bright star-like objects on a green background, When an electric field is applied the average time taken for the particles to travel a distance of one square on the eyepiece graticule can be easily measured. One particle is measured each time the field is applied for a short time (i.e. 10-205) and the polarity is then reversed and the speed in the opposite direction measured. TheEXPERIMENT 6.1 ZETA POTENTIAL MEASUREMENTS, 123 Quartz cell Lamp source Microscope Voltage supply Figure 6.17 Photograph of the Rank Bros MK2 microelectrophoresis instrument. polarity must be reversed each time and the field never left on for longer than about 30s, so that the possibility of polarization effects is reduced. Usually, between 10 and 20 particles in the field of view are measured and the average value obtained. The applied voltage should be varied to make the particles move over one square in about 10s but this voltage must never be increased above about 30 V. Be careful only to measure particles clearly in the plane of focus, since the microscope will have been set to measure at the fluid stationary plane within the rec- tangular cell. Particles not in focus will travel at a speed which will include a fluid flow component and will lead to experimental errors if included in the data. A photograph of a typical Rank Bros instrument is given Figure 6.17. Once the apparatus is set up, all you have to do is change the colloidal124 CHARGED COLLOIDS Figure 6.18 Rectangular quartz cell used to measure electromobility. solutions in the rectangular cell and measure their mobilities. Be careful to check the direction the particles move in, which denotes their sign of charge. This sign will change at some CTAB concentration. (As a guideline, in water the silica particles are negatively charged.) In order to change solutions, the electrodes are first carefully removed (very little effort should be required to do this — be careful, these cells are expensive) and are then stored in distilled water. The old solution is aspirated out and the cell rinsed and aspirated with distilled water, Finally, the new solution is poured into the cell and the elec- trodes carefully replaced so that no air bubbles are trapped near the electrodes. The new solution should be left to equilibrate (at 25°C) for about 15 minutes before measurement. A typical rectangular quartz cell is shown in Figure 6.18. The speed of the colloid particles is measured at a stationary fluid layer within the rectangular cell. These cells are expensive and must be handled carefully. At the end of the experiment the electrodes should be removed and placed in distilled water and the cell should be rinsed and filled with distilled water. The speed of the particles can be easily calculated using the fact that each square of the graticule corresponds to a known distance, typicallyy iPage rien Chemistry Notes for class 12 Chapter 2 Solutions Solution is a homogeneous mixture of two or more substances in same or different physical phases. ‘The substances forming the solution are called components of the solution. On the basis sa solution of two components is called binary solution. ‘of number of compon Solute and Solvent In a binary solution, solvent is the component which is present in large quantity while the other component is known as solute. Classification of Solutions (A) Following types of solutions are seen on the basis of physical state of solute and solvent. [Sotute [solvent [| __Examples Jaalid solutions — 1 Solie Sond Alloys 2 Laud Solid Hydrated salts, Amaigam ot Hg with 3 Gas Solid Dissolved gages in mineral ~ A quid solutions i en ae 4 Soli viquia Sait’sugar solution in water 5 Ligud Liquid Aiconol in. water 6 Gas Liguid | Aerated drinks. O. in water __. Leaseous solutions . = 7 Solid Gas ilodine vapeut in av : 8 Liquid Igas Water vapour in air ' 9 Gas Gas Air (s+ N9) [if water is used as a solvent, the solution is called aqueous solution and if not, the solution is called non-aqueous solution.) (B) Depending upon the amount of solute dissolved in a solvent we have the following types of solutions: (i) Unsaturated solution A solution in which more solute can be dissolved without raising temperature is called an unsaturated solution. www.ncerthelp.com (Visit forall ncert solutions in text and videos, CBSE syllabus, note and many more)(i) rated solution A solution in which no solute can be dissolved further at a given temperature is called a saturated solution (ii) Supersaturated solution A solution which contains more solute than that would be necessary to saturate tata given temperature fs called # supersaturated solution. Solubility ‘The maximum amount of a solute that ean he dissolved ina given amount of solvent (generally 100 g) at a given temperature is termed is its solubility at that temperature, ‘The solubility of a solute ina liquid depends upon the following factors: (i) Nature of the solute (ii) Nature of the solvent Femperature of the solution ‘Phe most commonly used form of Henry's law states “the partial pressure (P) of the gas in vapour phase is proportional to the mole fraction (x) of the gas in the solution” and is expressed as p=Ky.x Greater the value of Ky, higher the solubility of the gas. The value of Ky decreases with increase in the temperature, Thus, aquatic species are more comfortable in cold water [more dissolved Op] rather than Warm water, Applications 1, In manufacture of soft drinks and soda water, CO; is passed at high pressure to increase its solubility. 2. To minimise the painful effects (bends) accompanying the decompression of deep sea divers. Opdiluted less soluble, He gas is used as breathing gas. 3. At high altitudes, the partial pressure of O, is less then that at the ground level. This leads to Jow concentrations of O2 in the blood of climbers which causes ‘anoxia’. Concentration of Solutions The concentration of a solution is defined as the relative amount of solute present in a solution. On the basis of concentration of solution there are two types of solutions, (i) Dilute solution (ii) Concentrated solution www.neerthelp.com (Visit for all ncert solutions In text and videos, CBSE syllabus, note and many more)Page Methods of Expressing Concentration of Solutions Various expression for the concentrations of solutions can be summarised as (i) Percentage by weight (w / w %) It is defined as the amount of solute present in 100 g of solution. w/w %= weight of solute / weight of solution * 100 (ii) Percentage by volume (w / V%) It is defined as the weight 01 solute present in 100 mL of solution. w/V %= weight of solute / weight of solution * 100 or the volume of solute present in 100 mL of solution, u/V %= volume of solute / volume of solution * 100 (iii) Mole fraction (x) It is defined as the ratio of the number of moles of a component to the total number of moles of all the components. For a binary solution, if the number of moles of A and B are na and nprespectively, the mole fraction of A will be xe 4 ngtnp eet n Similarly, 4e=—— + ta taped ' . nat hp (iv) Parts per million (ppm) It is defined as the parts of a component per million parts (10) of the solution, It is widely used when a solute is present in trace quantities. ppm = number of parts of the component / total number of parts of all the components * 10° () Molarity (M) It is the number of moles of solute present in 1L(dm*) of the solution. M = mumber of moles of solute / volume of solution (L) M-= mass of solute (in gram) * 1000 / mol. wt. of solute x volume of solution (in mL.) Molarity varies with temperature due to change in volume of solution. [When molarity of a solution is 1 M, it is called a molar solution. 0.1 M solution is called a decimolar solution while 0.5 M solution is known as semi molar solution} Molarity = Percent by mass * density * 10 / molecular weight www.ncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more)fa|Page Dilution law, My Vj = Mz Vp (for dilution from volume V, to V2) For reaction between two reactants, My Vj /n) = Mz V2/ ny where, nj and n3 are stoichiometric coefficient in balanced equation. (vi) Molality (m) It is the number of moles of solute per kilogram of the solvent. Molality = mass of solute in gram * 1000 / mol. wt. of solute * mass of solvent (in g) Molality is independent of temperature. [When solvent used is water, a molar (1M) solution is more concentrated than a molal (1 M) solution.] (vii) Normality (N) The number of gram equivalents of solute present in 1 1 of solution. Nonnality = number of grams — equivalent of solute / volume of solution in L Number of gram-equivalerits of solute = mass of solute in gram / equivalent weight [Relationship between normality and molarity N x Eq. weight = Mx mol. weight ] If two solutions of the same solute having volumes and molarities V;, My and V2, Mz are mixed, the molarity of the resulting solution is Ma ViM+VMy, VYWtVy Similarly, Normality (My = NiVit NaVo Vy+Ve To dilute V; mL ofa solution having molarity M; to molarity My up to the final volume Vo mL, the volume of water added is Ve-¥, -(454). Similarly, V;-V, = (2) vy, 2 Formality (F) It is the number of formula weights of solute present per litre of the solution. Formality = moles of substance added to solution / volume of solution (in L)) www.ncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more)vage (ix) Mass fraction Mass fraction of any component in the solution is the mass of that component divided by the total mass of the solution, Molality, mole fraction and mass fraction are preferred over molarity, normality, etc., because former involve weights which do not change with temperature, (x) Demal (D) It represents one mole of solute present in 1L of solution at O°C. The Raoult’s law states “For a solution of two volatile liquids, the vapour pressure of each liquid in the solution is less than the respective vapour pressure of the pure liquids and the equilibrium partial vapour pressure of the liquid is directly proportional to its mole fraction. Fora solution containing two liquids A and B, the partial vapour pressure of liquid A is Pa=Xa OF PA = RK where, XY, = = mole fraction of liquid A — (ng + np) The proportionality constant is obtained by considering the pure liquid when x = 1 then k= 4, the vapour pressure of pure liquid, hence Pa = PALA similarly, Pp ® Poke The total vapour pressure of the solution, Pr = Pa + Pp= PA Xa * Pb kB “= Dh + (Pp Pata Konowaloff Rule At any fixed temperature, the vapour phase is always richer in the more volatile component as compared to the solution phase. In other words, mole fraction of the more volatile component is always greater in the vapour phase than in the solution phase. The composition of vapour phase in equilibrium with the solution is determined by the partial pressure of components. If Y; and Y; are the component | and 2 respectively in the vapour phase then. using Dalton’s law of partial pressure, Pi=yi* Protas wwwncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more)p2=y2* Prosat Ideal Solutions Those solutions in which solute-solute (B-B) and solvent-solvent (A-A) interactions are almost similar to solvent solute (A-B) interactions are called ideal solutions. These solutions satisfy the following conditions : (i) Solution must obey Raoult’s law, i.e., Pa = PALA» Pa = Paks (ii) AHmix = 0 (No energy evolved or absorbed) (iii) AVmix = 0 (No expansion or contraction on mixing) Some solutions behave like nearly ideal solutions, e.g., benzene + toluene. n-hexane + n- heptane, ethyl iodide + ethyl bromide, chlorobenzene + bromobenzene. Non-ideal Solutions Those solutions which shows deviation from Raoult’s law is called non-ideal solution. For such solutions, AH nix #0 AV ix # 0 (a) Non-ideal solutions showing positive deviation In such a case, the A —B interactions are weaker than A — A or B -B interactions and the observed vapour pressure of each component and the total vapour pressure are greater than that predicted by Raoult’s law. www.ncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more)Pa> PaXar Pn> PoXp Prat > PAXA + PaXB For such solutions AH yi > 0, AVinix > 0 Max + water: CS, Examples : Ethanol CCL, + CgH,CH,.-ethanol + eydohexane. CCL) + CHC]: + acetone, CCl, + Cle (b) Non-ideal solution showing negative deviation In such a case, the A —B interactions are stronger than A — A or B —B interactions and the observed vapour pressure of each component and the total vapour pressure are lesser than that predicted by Raoult’s law. Pa < PALA: Pa < Paks Pisa < Pa%a + Poke For such solutions, AB nix < 9, AVinix < 0Ol Page %A=1 Mole fraction a0 ta=0 yar Non-idaal solution showing negative deviation Examples : CHCl, +CH,COCH,, CHC), +C,Hg, H,0 + HCI, 1,0 +HNO,, methanol + acetic acid. Azeotropic Mixture A mixture of two liquids which boils at a particular temperature like a pure liquid and distils over in the same composition is known as constant boiling mixtures. These are formed by non- ideal solutions. () Minimum boiling azeotropes are formed by those liquid pairs which show positive deviation from ideal behaviour. Such azeotropes have boiling points lower than either of the components, ¢.g., CzHsOH (95.57%) + HzO (4.43%)(by mass). (ii) Maximum boiling azeotropes are formed by those liquid pain; which show negative deviation from ideal behaviour. Such azeotropes have boiling points higher than either of the components. ¢.g., H20(20.220%)+ HCI (79.78%] by mass. Colligative Properties {Colligatilte : from Latin. = Co mean ‘together’; ligare means ‘to bind” ] Colligative properties are those properties which depends only upon the number of solute particles in a solution irrespective of their nature, Relative Lowering of Vapour Pressure It is the ratio of lowering in vapour pressure to vapour pressure of pure solvent. The relative lowering in vapour pressure of solution containing a nonvolatile solute is equal to the mole fraction of solute in the solution. www.ncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more)Ph - APA a xy Pa where, 24-4 = relative lowering of vapour pressure Ph PADMA. Me pa nyt hp for dilute solutions, ny << ny. Hence, PAT Pa. Mp pm OMA © or Pia Pa. WaxMy PR Mg xW, My= = xM, x—PA— (Dh - Pa) Above expression is used to find the molecular weight of an unknown solute dissolved in a given solvent. Where, Wp and W, = mass of Solute and solvent respectively. Ms and Ma = molecular weight of solute and solvent respectively. Ostwald and Walker method is used to determine the relative lowering of vapour pressure. Elevation in Boiling Point (AT,) Boiling point ofa liquid is the temperature at which its vapour pressure becomes equal to the atmospheric pressure, As the vapour pressure of a solution containing a nonvolatile solute is lower than that of the pure solvent, it boiling point will be higher than that of the pure solvent as'shown in figure. The increase in boiling point is known as elevation in boiling point, AT, www.ncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more)qwyrage 1 Vapour pressure 3 5 Temperature —» AT, = Ty- Ty AT, = Ky m (where; m = molality) Ky is molal elevation constant or ebullioscopic constant. Molecular mass of solute can be calculated as K,- Wp x 1000 Ky: Wp x 1000 al, = ex Wa Wa , 1000 Moe kK, Exe BW” RT, where, Wp and Wa = mass of solute and solvent respectively. Ky has units of K/m or K kg mol", for water, Ky = 0.52 K kg mol The boiling point elevation of a solution is determined by (i) Landsberger’s method Gi) Cottrell’s method Depression in Freezing Point (AT;) Freezing point of a liquid is the temperature at which vapour pressure of the solvent in its liquid and solid phase become equal. As we know that vapour pressure of solution containing non-volatile solute is lower than that of pure solvent, solid form gets separated out at a lower temperature as shown in the figure. www.ncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more)Ty OT Temperature — This decrease in freezing point ofa liquid is known as depression in freezing point. Depression in freezing point (AT) = T’r— Tr Wp , 1000 AT, =K, Ky Pee Ma Wa To find molecular mass of solute, K, «Wz x 1000 Mt, = aT; Wa where, Ky is molal depression constant or cryoscopic constant. Khas units of K / m or K kg mol". Ethylene glycol is usually added to water in the radiator to lower its freezing point. It is called antifreeze solution. [Common salt (NaCI) and anhydrous CaC12 are used to clear snow on the roads because they depress the freezing point of water. The freezing point depression is determined by Beckmann method or Rast method.] Calculations of molal elevation constant (Ky) and molal depression constant (Ky) www.ncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more)JiajPage . 4yp. ‘ MART g Maney TE oe aH, AH, T, = boiling point of solvent T; = freezing point of solvent AH, = molar enthalpy of fusion AH,, = molar enthalpy of vaporisation Osmotic Pressure (7) Osmosis is the phenomenon of spontaneous flow of the solvent molecules through a semipermeable membrane from pure solvent to solution or from a dilute solution to concentrated solution. It was first observed by Abbe Nollet. Some natural semipermeable membranes are animal bladder, cell membrane etc. CU,[Fe(CN)]is an artificial semipermeable membrane which does not work in non-aqueous solutions as it dissolves in them. Osmosis may be (i) Exosmosis It is outward flow of water or solvent from a cell through semipermeable membrane. . (ii) Endosmosis It is inward flow of water or solvent from a cell through a semipermeable membrane. The hydrostatic pressure developed on the solution which just prevents the osmosis of pure solvent into the solution through a semipermeable membrane is called osmotic pressure. .. where, d= density, R = solution constant, T = temperature, My = molar mass of solute wwwncerthelp.com (Visit for all ncert solutions in text and videos, CBSE syllabus, note and many more) 403 - $59 -LLQfo raat ee CHEMISTRY NOTES ~ CHAPTERS 20 AND 21 Acids and Bases - Neutralization Goals : To gain an waderstunding of: ‘The properties of acids und bases nations, 1 3 Is anal bases 4 Ti Properties of ecids (HY or protons) in solution + Form hydrogen ater molecile bonded to a hydrogen ion shown as HO" or HHO) ions in aqueous © Form hydronium (x solution Have a low pH (below 7) Neutralize bases to form water aad a salt Have a sour taste Cause indicators to change color Are electrolytes (are ionic in nature) React with many metals to produce hydrogen yas (single replacement reaction) Properties of bases Form hydroxy! ions (OH) in solution Have a high pH (above 7) Neutralize acids to form water and a salt Have a bitter taste Feel slippery Cause indi ‘Are electrolytes (are s to change color ic in nature) Water is neutrul, not because it does not have any hydronium (acid) or hycroxyl ions (base) present, but because these ions are ‘equal in concentration (07 M). They re equal because pure water, even though it is covalently bonded. has some fonic character to form these ions according (o either of the following equativns. HO €9 HY + OH 2H,0 €> HO’ + OW Note : I will teat the hydrogen ion (H") and the hydronium ion (H,O*) as the same thing throughout these notes. ‘Neutral solutions have a pH of 7 and have equal concentrations of hydroniuin and hydroxyl ions (107 M).. ‘The pH ofa solution is the negative logarithm of the hydrogen ion concentration (pH = -log {H1"). The logarithm (base 10) of a number is the number to which ten must be raised to get that number. For example the log of «1 is -1 (1 = 10"). The pH scale is @ scale of 0 to 14 and indicates the measure of H ions present - the amount of acidity of a solution.f | Exponent PICIOR | peseription {ie | Notation | log my | 1 two | 0 | strong acid 4 tx10! esis aes | o bo? a2 [2 i 001 tat! 4 3 00 00001 neutral {H+} =| 1.0%107 | i | 000001 | 0000001 i | strong base | If the pH is less than 7 the solution is considered to be uc’ i ({H"} 1.0 x 10” and JOH}<1.0 x 10”) and ifthe pH is above 7 the solution is considered to be basic, or alkaline ({H"}<1.0 x 10° and !H'T>1.0 x 107), If the hydrogen ion (H") ion increases the hydroxide ion (OH') will decrease and vice versa. ‘The ion product constant for water (Ky) at 25 °C is 1.0 x 10" (moV/L)’. This comes from the equation for the sc: wunization of water shown above. Kw= (H*}(OH]= 1.0x10"(moVL)? = (1.0x 107 moV/L)(1.0 x 107 moV/L) = 1.0.x 10™(moV/L?? “This equation can be used to calculate (H*] or {OH'| as follows: ‘What isthe [H+] of an aqueous solution at 25 °C if the [OH-]is 2.56 x 10% Rearranging Kw=[H+] [OH-| to solve for [H+] we 10x10" not piy}= 39x10" Me 56x10) mh “The equation to solve for pH from [H" is pH = -log (H"}. Here is an example. What is the pH{ of a solution in which the [H+] is 1.12 x 10 moVL? | pmo ues oe aerty =3.95The equation to solve for [N°] from pl is (HT = 10" solve for 11°] from pl is {1} = 10, Here isan example ov ie Ke (" a Kl) | What is the [H+] of a solution which has a pit of 6.5 7 l +} = 109" = 1085 ©3210" mol, ‘Another equation to solve for pH (or [H"}) can be derived from the equation for the ion product constant of water (K,.). Algebraically we can take the log of both sides ofthe equation for Kw to get the equation pK, =pll + pol pk 4.00 therefore the ubove equation can be rewritten as 1400= pl + pOH ‘ich can be a handy equation to solve for pH from pOH or vice vers. here isan example stating from the hydroxide ion concentration, - What is the pH of a solution which has a [OH-] ion concentration 0f 3.0.x 10 moVL? POH = -loglOHL| = -og (3.0.x 10) = 5.5 Rearranging 14.00 = pH + pOH to solve, fim get pH = 14.00 - pOH solving: pH = 14.00-5.5=8.5 Svante Arthenius (Sweden, 1887) proposed that acids are substance which yield hydrogen ions (Hs) in aqueous solution and ‘bases are substances which yield hydroxide (OH-) ions in aqueous solution. Examples of Archenius acids are hydrochloric acid HC), sulfuric acid (H,SO0), and phosphoric acid (HsPO.). Examples of Arrhenius bases are hydroxide (NaOH), calcium hydroxide (Ca(OH),), and aluminum hydroxide (AK(OH)3) 3 “Monoprotic acids have only one fonizable hydrogen ion (proton). Examples are hydrochloric acid (HC) and nitric acid (HNO). Diprotic acids have two ionizable hydrogen ions. Examples are sulfuric acid (H,SO«) and carbonic acid (H;CO3). Triprotic acids have three ionizable hydrogen ions. An example is phosphoric acid (H;PO,). Only the hydrogens involved in very polar or ionic bonds will ionize to form ions. These are hydrogens that are bonded to highly electronegative elements found in the upper right hand side ofthe periodic table. lonizable hydrogens are more electropositive and are generally written asthe first element in the formula of a compound. For example in the formula for acetic acid (HCH303) ‘only the first hydrogen (in blue) is ionizable, ‘The Bronsted-Lowry definitions of acids and bases are that acids are proton (hydrogen ion) donors and bases are proton ‘acceptors. All Arthenivs acids and bases are included in the definitions of Bransted-Lowry definitions, but there are some Bronsted-Lowry acids or bases that are not Antenius acids or bases. For example ammonia (NH) is not an Arrhenius base - it does not form OH. ions (in the equation below water provides the OH- ion). It is a Bronsted-Lowry base because it will accept a hydrogen ion as shown in the following equation, NH; + H,0 5S NH! + OW AE Xx ‘ammonia - accepts Ht water - donates H+ va (Bronsted-Lowry base) (Bronsted-Lowry acid) ‘A conjugate acid i the substance formed when a Bransted-Lowry base accepts a hydrogen ion. A conjugate base is the substance formed when a Bronsted-Lowry acid donates a hydrogen ion. Inthe above equation the ammonium ion (NH,+) isthe conjugate sci formed bythe Brosted-Loiry base annua (NH sing vhs! ics au (UAL) ds the NUKE : ‘beoustedsLowry acid water donating a hydrogen ion. Conjugate acids and bases are always writen on the 1G BR 08product side of a chemical equation. Conjugate acids behave just as a Bronsted-Lowry acid in the reverse direction (donate hydrogen ions) and conjugate bases behiwve just as Bronsted-Lowry bases inthe reverse direction, Here is another example. HCO, + H,0 11,0° HCO; acid base conjugate conjugate ; “a bas Amphotre substances ae substances which en acts both an ai and a bas, An examples water, Water whenit self ones forms a hydrogen ion (acid) and a hydroxide ion (base). ° 7 ‘Acids and bases can be classified as trong or weak depending on the extent to which they ionize. Strong acids and bases ionize to a large extent to form many hydrogen or hydroxide fons and have a large acid or base dissociation constant (Ka or Kb). Weak acids or bases ionize toa small extent to form few hydrogen or hydroxide ions and have a small Ka or Kb. An example of a weak ‘cdi aati ci. It wil form few hydrogen igns and most of the acid stays in the undssocated form as shown in the equation low. 2 + 1,0 = 130° + C,H,G5 ‘The larger arrow and fewer hydronium ions being formed. tes thatthe equilibrium position lies tothe left indicating more undissociated acid Here is another way to picture the difference between a strong and weak acid. HA is the undiss dissociated hydrogen ions and A- indicates the dissociated anion of the acid. Strong — E Gracies HA Weak acid jated acid, H+ indicates the HA Diprotic and triprotic acids dissociate stepwise, meaning all the hydrogen ions do not dissociate simultaneously. For example phosphoric acid (H,PO,) would dissociate in three steps : a. HPO, €9 Ht + HPOs b. HPO; €3 HY + HPO,? < HPO,? €3 HY + PO? 7 © step a would be the have the largest Ka, Each sucessive step would have a smaller Ka as it becomes increasingly difficult to remove a positive hydrogen ion from a more negative anion. ‘trong and weak in relation to acids and bases. hoes will fonize, The romcenteated and (MULE su. wes = 1 with the Concentrated and due i.» * Sehye-s + present. not the exten ww : following diagrams should ilustrate the ditferences. HA relers tu the Undissocisted acid, H’ indicates the hydrogen 1ons aun lates the anion of the acid.HAA 7 alll Wa HAHA nA it K MAA HA MA na Wt HA n WA yl uy wt MAMA HA | Concentrated weak Ditute weak acid- pitt strong acid - | litte acid present much acid present with lite disseiation qith a high degree of acid of dissociation many hydrogen ions Neutralization reactions a actions between acid and bases. In aqueous solution neutralization reactions produce a salt and water. The generalized equ on is thus : acid + base > salt + water re are some specitic examples : - HCl © eae « wattle Palle eae HHO - H,PO, + 3Ni a tient 5 ant, 3? aenllB Oe, tay? HHO HySO, + Ca(OH), > CaSO, + 2,0 Suwiaid” + eiumydmnize > ealsamsulte + Water ‘The term “neutralization” can be misleading. Not all neutralization reactions result in a neutral solution. Only neutralization reactions which have equivalent amounts of hydrogen ions and hydroxide ions from acids and bases will result in neutral solutions. The balanced equation and a little bit of stoichiometry can be used to calculate the equivalent number of moles needed. Here is an example of such a calculation : ()Write and balance the equation for the neutralization of carbonic acid by lithium hydroxide and then (2) determine the number of moles of lithium hydroxide needed to neutralize 1.12 moles of carbonic acid. “1, H,CO, + 21i0H —> 1i,CO; + 21,0 2. Using the male ratio from the balanced equation : Ln T,CO, Gee Lion. =2.24 mol LiOH KT marsCO, Titration is a powerful analytical tool used to determine the concentration of an unknown from the concentration of a known (standard) solution. Four steps are needed to perform the calculations of a titration between an acid and a base. 1, Write and balance the neutralization reaction, 2. Determine the number of moles used of the standard (known) solution. (moles = M x V) 3. Determine the number of moles present in the unknown using the mole ratio from the balanced equation. 4, Determine the molarity (moles/L) of the unknown from step 3 and the volume of the unknown given in the problem. Here is an example.«500 ma (- 05001) solution of HCI which is NSOL)of 2080 M (mo) solution of Ca(O1,? LAHCL + CoOI), => CaCl, + 21,0 2. ogy (SOs). ora exon, son renown, (a a, * 226 matnc1 £26 mol HCL 4 SalI Ss MHL Buffers are substances or combinations of substances which keep pH levels fairly constant when small amounts of acid or base are added. Buffers are formed from the combination of a weak acid and one of its salts or a weak base and one of its salts. An example ofa buffer is acetic acid (weak) and sodium acetate, a salt of acetic acid Ifa small amount of acid is added to a system Containing these substances the hydrogen ion from the acid will react with the acetate ion from the sodium acetate to form Uundissociated acetic acid effectively removing the hydrogen ion to keep pH constant : H+ Chor > HEM, Ifa base is added the OH- ion from the base will react with the acet the added OH- ion : id to form water and the acetate ion to effectively remove OH- + HCHO, > HO + CyH,O; So, whether acid or base are added they are removed to keep pH constant, ‘The common ion effect is the lowering of the solubility of a substance_by the addition of a common ion. This can be easily seen in relation to LeChatelier’s principle. At equilibrium a slightly soluble salt such as silver carbonate will be saturated. AgiCO, 5 2 Ag” + CO;? If silver iodide (Agl) is added to the system it will increase the [Ag+] - the common ion - and cause the reaction to shift to the left. This is the undissociated, or non dissolved, state indicating the lowering of the solubility of the silver carbonate. Acids and Bases Properties of Acids and Bases L Acids ‘A. Properties of Acids 1. Aqueous solutions of acids have a sour taste 2. Acids change the color of acid-base indicators 3. Some acids react with active metals to release hydrogen Za(s) + H;SO4(aq) > ZnSO«(eq) + Hi(e) 4, Acids react with bases to produce salts and water (neutralization) HCl(aq) + NaOH(aq) -> NaCl(aq) + H,0() 5. Aqueous solutions of acids conduct electric current (they are electrolytes) IL. Some Common Industrial Acids A H.SO; - Sulfurie Acid 1. Use ning sess 2. Aaya production ci B. HNO) - Nitric Acid 1. Unstable, volatile liquid in pure state 2. Yellowing caused by the formation of nitrogen dioxide gas inthe US. + nesdwets, car batteries3. Used in making fertilizers, explosives, vubber, plastics, pharmaceuticals 4. Stains skin and other proteins yellow .1yPO, - Phosphoric Acid 1. Nota common laboratory acid 2. Flavoring agent in sodas 3. Usa in making fertilizers and detergents D.HICI-Hydrochiovie Acid 1. TICT in the stomach aids the digestion of proteins 2. Used in pickling steel, recovering magnesium from sea water, leaning masonry and correcting. pool pH . Acetic Acid 1. Acid component of vinegar 2.Concentrated "glacial" acetic acid used in making chemicals for plastic manufacturing TIL. Bases A. Properties of Bases 1. Aqueous solutions of bases have a bitter taste 2. Bases change the color of acid-base indicators 3. Dilute aqueous solutions of bases feel slippery 4, Bases react with acids to produce salts and water 5. Aqueous solutions of bases conduct electric current (they are electrolytes) IV, Arrhenius Acids and Bases Svante Arrhenius, Swedish chemist (1859-1927) A. Arthenius Acid 1, A chemical compound that increases the concentration of hydrogen ions, H’, in aqueous solution B. Ambenius Base 1. A substance that increases the concentration of hydroxide ions, OH’, in aqueous solution . Aqueous solutions of acids 1. Acids are molecular compounds that ionize in solution HNO; + HO > H;0' + NOs H2SQu + Hx > HsO" + HSOr HO + HCl > Hy’ + Cl $)-LO}- DW D. Strength of Acids 1. Strong acids ionize completely in solution and are strong electrolytes 2. Weak acids ionize only slightly and are weak electrolytes Weak acidsBronsted-Lowry Acids and Bases 1. Bronsted-Lowry Acids and Bases ‘A. Bronsted-Lowry Acid 1. Amolecule or ion that is a proton donor (a proton is a hydrogen ion H") B. Bronsted-Lowry Base 1. A molecule or ion that isa proton acceptor C. Bronsted-Lowry Acid-Base Reaction 1. A reaction in which protons are transferred from the ucid to the base 11. Conjugate Acids and Bases A. Conjugate Base 1. The species that remains after an acid has given up a proton HPOdaqh + H,O() + HyO"(aq) + HPOL(ag) ald conjugate base B. Conjugate Acid 1. The species that is formed when a base gains proton HPOxaq + HO) Hy0'(aq) + HPOLaq) ~ base conjugate acid IIL, Amphoterie Compounds ‘A. Amphoteric 1. Any species that can react as either an acid or a base a. Water as a base HsPOuaq) + HrOil > HiO'{ag) + HePOAaq) b. Water as an acid Nie) + H,O() & NH j(ag)+ OH“(ag) . Water as both an acid and a base H,0 + H,0 > 0° + OW H,0° is called the hydronium ion and is what actually exists in an acidic solution. ‘There are no free H° ions Neutralization Reactions I, Strong Acid-Strong Base Neutralization ‘A. Neutralization 1. The reaction of hydronium ions and hydroxide ions to form water molecules B. Neutralization Rxns KOH(aq) + HNOs(aq) > KNO;(2q) + H:0(1) II, Acid Rain ‘A. Formation of Acid Rain 1. Nonmetallic oxides enter the atmosphere as a result of coal burning, auto exhaust, other forms of air pollution $02 ,S0;,CO,, NO, NO, 2, Nonmetallic oxides combine with water to form oxyacids SOs(g) + H,0(1) > HSO«(aq) B. Reactions of Acid Rain 1. Reaction with marble (metamorphic calcium carbonate) CaCO\(s) + 2H;0"(aq) > Ca”'ag) + CO,(g) + 3H;0(1)Aqueous Solutions and the Concept of pH 1. Hydronium fons and Hydroxide Tons A.Sel-lonization of Water 1. Autoprotolysis H,0() + H,0() > H,0"aq) + OH (ag) @ Bog OG} - Dg B. loniaation Constant for Water (Ky) H,0°}}0H ] = (1.0 x 10”)(1.0 x 10") = 1.0.x 10 2. Kw is a constant at ordinary ranges of room temperatures . Neutral, Acidic, and Basie Solutions 1. Neutral a.[H,0°]=[0H] (pH 2. Acidic a.[Hs0']> [0H] (pH <7.00) - 3. Basie . a.[H,0']> [OH] (pH > 7.00) 7 .00) : IL, The pH Scale ApH 1. The negative of the common logarithm of the hydronium ion concentration a. pH =- log (H30*] B. poll I. The negative of the common logarithm of the hydroxide ion concentration a. pOH =- log [OH] PH + pols 140 © Thepht scaly Iculations Involving pH A. Calculation of pH from (H,0") Concentration See worksheet Determining pH and Titrations 1. Indicators and pH strips ‘A. Acid-Base Indicators 1, Compounds whose colors are seusitive to pH B. Transition Interval 1. pH range over which an indicator color change occurs 2. Indicators are useful when they change color in a pH range which includes the endpoint ofthe reaction C. Choosing Indicators (indicator must change color atthe proper pH) IL, Acid-Base Titration A. Titration 1 Controlled addition ofthe measured amount of a solution of a known concentration required to react completely Will a wieaoured aits ov! of solution of unknown concentration B, Equivalence Point 1. The poiat at which the solutions used ina titration are present in chemically equi C. Titration Curves 1. End point ‘a, the point in a titration at which the reaction is just completed (mol acid = mol base) ent amounts (equal mols)